CHNG TRNH MN HC

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Thng tin ging vin

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Thng tin mn hc
Tn hc phn: Ha hc i cng A2 MSMH: HH002 S VHT: 03 (45 tit l thuyt) Hc phn tin quyt: Ton Gii tch, Vt l i cng

Mc tiu chung ca mn hc
Trang b cc kin thc nn tng, c bn ca Ho hc.

Hnh thc nh gi
Cn c vo quyt nh 252 ca Hiu trng Trng i Hc Bc Liu C th: C mt trn lp t nht 33 tit Tham d y 1 bi kim tra gia hc phn theo yu cu im trung bnh hc phn: TBHP = (A x 3 + B x 7) : 10

Trong : A: im TBKT B: im thi kt thc hc phn 1

im thnh phn v im thi u lm trn n phn nguyn thang im 10

Chng trnh c th
Ni dung Chng 1 Nguyn l th nht nhit ng hc v p dng vo ha hc Chng 2 Nguyn l th hai nhit ng hc, chiu v gii hn t din bin ca qu trnh Chng 3 Cn bng ha hc Chng 4 Cn bng pha Chng 5 Dung dch Chng 6 Dung dch cht in ly Chng 7 ng ha hc Chng 8 Cc qu trnh in ha Tit 6 6 4 4 4 6 8 7

Ti liu tham kho

(1) Ho i cng Nguyn nh Soa Trng i hc Bch Khoa Thnh ph H Ch Minh. (2) Ho V c (Tp 1) Hong Nhm Nh xut bn Gio dc. (3) Ho i cng N. L. Glinca (bn dch) Nh xut bn Gio dc.

Chng 1 NGUYN L TH NHT NHIT NG HC V P DNG VO HA HC

------

I MC TIU

Sinh vin nm c mt s khi nim c bn v nhit ha hc. Xc nh c bin i ni nng U, bin i entalpi H ca mt qu trnh

cng nh nhit phn ng ha hc. Sinh vin nm c cc ng dng ca nh lut Hess, cc h qu v s ph

thuc ca hiu ng nhit vo nhit .

II NI DUNG CHI TIT

1
1.1

Mt s khi nim m u
Kh l tng Cht kh c coi l l tng khi m khong cch gia cc phn t kh xa nhau, c th b qua s tng tc gia chng v coi th tch ring ca cc phn t kh l khng ng k (kh c p sut thp). Phng trnh trng thi ca kh l tng: Nu c n mol kh p sut P, nhit T v chim th tch V th: PV = nRT =
m RT M

(1.1)

Trong : m: Khi lng ca kh, g M: Khi lng mol ca kh, g T: Nhit tuyt i, K ( T = tC +273) R: Hng s kh l tng, ty theo n v ca P v V m c ga tr khc nhau:

 Nu trong bnh c mt hn hp kh th mi kh gy nn mt p sut gi l p sut ring phn ca kh v c k hiu l Pi .Tng tt c cc p sut ring phn bng p sut chung P ca hn hp.Nu gi V l th tch chung ca hn hp kh (bng dung tch bnh ng th phng trnh kh kh l tng c dng:

1.2

H v mi trng H: H l i tng cn nghin cu cc tnh cht nhit ng hc. i km vi khi nim h l khi nim mi trng xung quanh, l ton b phn cn li ca v tr bao quanh h. H c phn cch vi mi trng xung quanh bng mt mt thc hay tng tng. C 4 loi h

H c lp l h khng trao i cht v nng lng vi mi trng. H m l h trao i cht v nng lng vi mi trng. H kn l h ch trao i nng lng vi mi trng. H khng trao i nhit vi mi trng c gi l h on nhit. Quy c v du trong qu trnh trao i nng lng Nng lng trao i gia h v mi trng c th l cng, nhit, nng lng in, . H nhn nng lng: du (+) H nhng nng lng: du () 4

1.3

1.4

Trng thi ca h v cc thng s trng thi Trng thi v m ca mt h c c trng bng nhng i lng xc nh nh: tC, P, V, C, .... Cc thng s ny c th o c, gi l cc thng s trng thi. V d: Gia s mol kh n, nhit T v p sut P ca mt h kh (gi s l kh l tng) c mi quan h cht ch, c biu din bng phng trnh trng thi ca kh l tng PV= nRT. C hai loi thng s trng thi: dung v cng
Thng s trng thi dung l nhng thng s trng thi t l vi lng cht,

v d th tch, khi lng.

Thng s trng thi cng khng t l vi lng cht, v d nhit p

sut, nng , nht. 1.5 Trng thi cn bng ca h L trng thi ti cc thng s trng thi ca h khng i theo thi gian. V d phn ng thun nghch CH3COOH + C2H5OH <=> CH3COOC2H5 + H2O t trng thi cn bng khi nng ca 4 cht khng bin i. 1.6 Bin i thun nghch v bin i bt thun nghch Nu h chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc v cng chm qua lin tip cc trng thi cn bng th s bin i c gi l thun nghch. y l s bin i l tng khng c trong thc t. Khc vi s bin i thun nghch l s bin i bt thun nghch. l nhng bin i c tin hnh vi vn tc ng k. Nhng bin i xy ra trong thc t u l bt thun nghch. 1.7 Hm trng thi Mt hm F( P,V,T, ...) c gi l hm trng thi nu gi tr ca n ch ph thuc vo cc thng s trng thi ca h m khng ph thuc vo cch bin i ca h. V d: n mol kh l tng:
trng thi 1 c c trng bng P1V1= nRT1

 trng thi 1 c c trng bng P2V2= nRT2

PV l mt hm trng thi, n khng ph thuc vo cch bin i t trng thi 1 sang trng thi 2. 1.8 Nhit v cng L hai hnh thc trao i nng lng. Cng W (J, kJ); Nhit Q (J, kJ) Cng v nhit ni chung khng phi l nhng hm trng thi v gi tr ca chng ph thuc vo cch bin i. Cng gin n (cng chuyn dch).

Nu gin n bt thun nghch: Gin n chng li Pn khng i:

2
2.1

Nguyn l th nht nhit ng hc p dng vo ha hc

Khi nim ni nng U Nng lng ca h gm 3 phn: ng nng chuyn ng ca ton h. Th nng ca h do h nm trong trng ngoi. 6

 Ni nng ca h. Trong nhit ng ho hc nghin cu ch yu ni nng. Ni nng ca h gm: ng nng chuyn ng ca cc phn t, nguyn t, ht nhn v electron (tinh tin, quay, ...). Th nng tng tc (ht v y) ca cc phn t, nguyn t, ht nhn v electron. Nh th ni nng (U) ca h l mt i lng dung , gi tr ca n ch ph thuc vo trng thi vt l m khng ph thuc vo cch chuyn cht ti trng thi . N l mt hm trng thi. Ni nng ca h ph thuc vo bn cht, lng ca n, p sut, nhit , th tch v thnh phn. i vi kh l tng ni nng ca h ch ph thuc vo nhit . 2.2 Pht biu nguyn l th nht ca nhit ng hc Nguyn l th nht ca nhit ng hc v thc cht l nh lut bo ton nng lng: Nng lng ca mt h c lp lun lun bo ton. Tn ti mt hm trng thi U gi l ni nng, dU l mt vi phn ton phn. S bin i ni nng U ca h kn chuyn t trng thi 1 sang trng thi 2 bng tng i s ca tt c cc nng lng trao i vi mi trng trong qu trnh bin i ny (d l bin i thun nghch hay bt thun nghch).

i vi mt bin i v cng nh:

i vi mt bin i hu hn:

2.3 2.3.1

Nhit ng tch, nhit ng p Nhit ng tch (V = const) Xt 1 h kn, c T, V = const, h ch sinh cng c hc:

Qv l nhit ng tch, gi tr ca n ch ph thuc vo trng thi u v cui ca h. 2.3.2 Nhit ng p (P = const) Xt h kn, thc hin c T, P =const, h ch sinh cng c hc:

H c gi l entapi, n l hm trng thi v U v PV u l nhng hm trng thi.

3
3.1

Nhit phn ng ha hc
Nhit phn ng L nhit lng thot ra hay thu vo khi phn ng xy ra theo ng h s t lng, cht tham gia v sn phm cng mt nhit T. 8

 c th so snh nhit ca cc phn ng cn ch r iu kin phn ng xy ra: Lng cc cht tham gia v sn phm to thnh theo h s t lng. Trng thi vt l ca cc cht. Vi mc ch ny ngi ta a ra khi nim trng thi chun. Trng thi chun ca mt cht nguyn cht l trng thi l hc di p sut 101,325 kPa (1atm) v nhit kho st n bn nht. V d: Cacbon tn ti hai dng th hnh l graphit v kim cng. 298K v di p sut 101,325 kPa, graphit l bin i th hnh bn nht do trng thi chun 298K ca cacbon l graphit.
Nu phn ng c thc hin P = const th nhit phn ng c gi l nhit

phn ng ng p Qp = H.
Nu phn ng c c thc hin V = const th nhit phn ng c gi

l nhit phn ng ng tch Qv = U. Phn ng ta nhit v phn ng thu nhit

Phn ng ta nhit: L phn ng nhng nhit lng cho mi trng. Khi

H = Qp < 0 hoc U = Qv < 0. V d phn ng ti vi, ....

Phn ng thu nhit: L phn ng nhn nhit lng t mi trng. Khi

H = Qp >0 hoc U = Qv > 0. V d phn ng nung vi, .... Quan h gia nhit ng tch v nhit ng p:

3.2

Nhit sinh chun ca mt cht 9

L nhit ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun (cht sn phm v cht phn ng phi l cc cht nguyn cht 1atm v gi P, T = const, cc s liu nhit ng chun trong cc ti liu thng c xc nh nhit T = 298K).

3.3

Nhit chy chun ca mt cht L nhit ca qu trnh t chy han ton 1 mol cht bng O2 to thnh cc oxit bn nht (vi ha tr cao nht ca cc nguyn t), khi cc cht trong phn ng u nguyn cht P = 1atm v gi T, P khng i (thng T = 298K).

4
4.1

nh lut Hess v cc h qu
Pht biu Hiu ng nhit ca mt phn ng ch ph thuc vo trng thi u v trng thi cui ca cc cht tham gia v cc cht to thnh ch khng ph thuc vo cc giai on trung gian, nu khng thc hin cng no khc ngoi cng gin n.

10

4.2

Cc h qu H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch nhng ngc du.

H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht cui tr i tng nhit sinh ca cc cht u.

T nh ngha ny suy ra: Nhit sinh ca mt n cht bn vng iu kin chun bng khng:

H qu 3: Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht u tr i tng nhit chy ca cc cht cui.

11

4.3

Cc ng dng nh lut Hess v cc h qu ca n c mt ng dng rt ln trong ho hc, n cho php tnh hiu ng nhit ca nhiu phn ng trong thc t khng th o c. V d 1: Khng th o c nhit ca phn ng Cgr + 1/2O2(k) = CO(k) v khi t chy Cgr ngoi CO (k) ra cn to thnh CO2(k) nhng nhit ca cc phn ng sau y o c:

tnh c nhit ca phn ng trn ta hnh dung s sau:

Trng thi u (Cgr + O2) v trng thi cui (CO2(k)) ca c hai cch bin i l nh nhau, do theo nh lut Hess:

V d 2: Xc nh nng lng mng lui tinh th ca NaCl(r) bit

12

 xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born Haber:

5
5.1

S ph thuc hiu ng nhit vo nhit . nh lut Kirchhoff

Nhit dung mol ca 1 cht L nhit lng cn thit nng nhit ca 1 mol cht ln 1K v trong sut qu trnh ny khng c s bin i trng thi (nng chy, si, bin i th hnh, ...).

5.2

Nhit chuyn pha Chuyn pha: bay hi ,nng chy, ng c, thng hoa, ...

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 Hcf l nhit lng trao i vi mi trng khi 1 mol cht chuyn pha. P = const, khi mt cht nguyn cht chuyn pha th trong sut qu trnh chuyn pha, nhit khng thay i. 5.3 nh lut Kirchhoff Xt 1 h kn, P = const. Xt phn ng sau thc hin bng hai con ng:

5.4

Mi quan h gia nng lng lin kt v nhit phn ng C th quy uc nng lng lin kt (Elk) tng ng vi nng lng ph v lin kt hoc hnh thnh lin kt. y ta qui c Elk ng vi qu trnh ph v lin kt: 14

nng lng lin kt l nng lng ng vi qu trnh ph v lin kt do nng lng lin kt cng ln th lin kt cng bn. Mt phn ng ho hc bt k v bn cht l ph v lin kt c v hnh thnh cc lin kt mi do Hp c th c tnh qua Elk ca cc lin kt ho hc. V d 1: Ph v 1 mol thnh cc nguyn t c lp:

III H THNG CU HI N TP
Cu 1: Cho 100 g N2 0C v 1 atm. Tnh Q, U, A trong nhng qu trnh: a. Nn ng tch thun nghch n 1,5 atm. b. Gin n ng p n th tch gp i. Chp nhn N2 l kh l tng v trong hai qu trnh trn nhit dung khng i, Cp = 6,96 cal.-1.mol-1. Cu 2: Tnh Q, U, H, A trong qu trnh a 2 mol kh l tng t V1 = 24,436 lt, p1 = 1 atm n V2 = 16,318 lt, p2 = 2 atm. Ly Cp = 7 cal.-1.mol-1. Cu 3: Xc nh th tch cui ca h v tnh cng trong qu trnh gin n on nhit thun nghch 10 lt khi He t 10 atm n 1 atm. Xem kh He nh kh l tng v ly
CV , He = 3 R. 2

Cu 4: Ti sao ni nh lut Hess l trng hp ring ca nguyn l th nht. Cu 5: Ti sao ni i vi kh l tng qu trnh ng tch v ng nhit hoc qu trnh ng p v ng nhit l qu trnh on nhit.

15

Cu 6: Mt hn hp kh A v B gm 0,495 g A c phn t khi 66 v 0,182 g B c phn t khi 45,5. p sut tng qut l 76,2 cmHg. Tnh p sut ring phn ca A v B. Cu 7: Hi aceton phn hy theo CH3COCH3(h) = C2H4 + CO + H2. Cho p sut ban u ca hi aceton l 1 atm, p sut chung ca hn hp l 2 atm. Xc nh hiu sut phn hy ca aceton. Cu 8: Xc nh nhit t c khi gin n thun nghch on nhit 1 mol khng kh t p1 = 20 atm, t1 = 0C n p2 = 1atm. Cho bit i vi khng kh
Cp CV = 7 . 5

16

Chng 2 NGUYN L TH HAI NHIT NG HC, CHIU V GII HN T DIN BIN CA QU TRNH
--- ---

I MC TIU
p dng nguyn l th hai vo ha hc, cung cp nhng kin thc c bn gip sinh vin tin on mt phn ng ha hc c th xy ra c hay khng mt iu kin xc nh no .

II NI DUNG CHI TIT

1 M u
Trong t nhin, cc qu trnh l hc v ho hc xy ra theo chiu hon ton xc nh. Nhit t truyn t vt nng sang vt lnh hn. Kh t truyn t ni c p sut cao n ni c p sut thp. Cc phn ng ho hc t xy ra, v d: Zn + HCl --> ZnCl2 + H2 Cn cc qu trnh ngc li th khng t xy ra c. Nguyn l th nht cho php tnh nhit ca cc phn ng nhng khng cho php tin on chiu v gii hn ca qu trnh. Nguyn l th hai cho php gii quyt cc vn ny.

2
2.1

Nguyn l th hai nhit ng hc. Hm entropy

Nguyn l th hai (tiu chun xt chiu ca qu trnh) Tn ti mt hm trng thi gi l entropi (S). nhit T khng i, trong s bin i v cng nh, h trao i vi mi trng mt nhit lng Q th bin thin entropi ca qu trnh c xc nh: 17

 Nu l bin i thun nghch:

Nu l bin i bt thun nghch:

Tng qut

Ch V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc l:

xc nh Sbtn, trc ht hnh dung mt qu trnh thun nghch c cng trng thi u v trng thi cui vi qu trnh bt thun nghch, sau tnh S theo cng thc:

2.2

Nguyn l th hai p dng trong h c lp i vi h c lp: Qtn = 0 --> S = 0 Qbtn = 0 --> S > 0 Nh vy i vi h c lp: Trong qu trnh thun nghch (cn bng), entropi ca h l khng i. Trong qu trnh bt thun nghch ngha l t xy ra, entropi ca h tng.

18

iu ny c ngha rng trong cc h c lp, entropy ca h tng cho ti khi t ti gi tr cc i th h t ti trng thi cn bng. o li ta c th ni: Trong h c lp: Nu dS > 0 ( S tng) h t din bin. Nu dS = 0, d2S < 0 (S max) h trng thi cn bng. 2.3 2.3.1 ngha hm entropy Entropy l thc hn n ca h Xt 1 h c lp T = const, h gm 2 bnh c th tch bng nhau, ng 2 kh l tng A v B c pA = pB u thp. Hai bnh c ni vi nhau bng mt dy dn c kho K. M K--> 2 kh khuch tn vo nhau cho n khi c s phn b ng u trong ton b th tch ca 2 bnh. S khuch tn cc kh l tng vo nhau l qu trnh c T = const (Q = 0) --> S > 0 (S2 > S1) --> hn n ca trng thi cui (hn hp 2 kh) c trng bng S 2 ln hn hn n ca trng thi u ( mi kh 1 bnh ring bit) c trng bng S1. Vy trong h c lp, qu trnh t xy ra theo chiu tng hn n ca h (tng entropi, S > 0). Qu trnh ngc li: Mi kh t tch ra khi hn hp kh tr li trng thi u khng th t xy ra. Kt lun Entropi c trng cho hn n: hn n ca h cng ln th S cng ln. Nu s ht trong h cng ln --> hn n cng ln --> S ln. Lin kt gia cc ht trong h cng yu --> hn n cng ln --> S ln. V d

S l hm trng thi v l i lng dung . 2.3.2 ngha thng k ca S Trng thi ca mt tp hp bt k c th c c trng bng 2 cch:

19

 Bng gi tr ca cc tnh cht o c: T, P,C, ... --> c gi l cc thng s trng thi v m. Nhng c trng nht thi ca cc phn t to nn h c gi l cc thng s vi m. S thng s trng thi vi m ng vi mt trng thi v m c gi l xc sut nhit ng . Nu s phn t trong h tng th S tng --> tng. Gia S v c quan h vi nhau thng qua h thc Bolzomann. H thc Boltzmann (l c s ca nguyn l th ba). S = kln k: hng s Boltzmann Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng . 2.4 2.4.1 Bin thin entropy ca mt s qu trnh Bin thin entropy ca qu trnh bin i trng thi ca cht nguyn cht Trong sut qu trnh ny T = const ==> S ca mt mol cht nguyn cht trong qu trnh bin i trng thi xy ra P = const l:

2.4.2

Bin thin entropy ca qu trnh gin n ng nhit kh l tng T = const, dn n n mol kh l tng t V1-->V2

Nu P1 > P2 --> S > 0: qu trnh gin n ny t din bin.

20

==> Cch pht biu khc ca nguyn l th hai: Cc cht kh c th t chuyn di t ni c p sut cao n ni c p sut thp. 2.4.3 Bin thin entropy ca cht nguyn cht theo nhit un nng n mol 1 cht nguyn cht t nhit T1 --> T2 vi iu kin trong khong nhit cht ny khng thay i trng thi. Trong iu kin P = const

Trong iu kin V= const

Nguyn l th ba nhit ng hc
Nhn xt: dng tinh th hon ho ca mt cht nguyn cht OK ng vi 1 trng thi v m ch c 1 trng thi vi m ==> OK th = 1.

3.1

Nguyn l th ba (tin Nernst) Entropi ca mt cht nguyn cht di dng tinh th hon ho OK bng khng:

3.2

Entropy tuyt i ca cc cht nguyn cht cc nhit T V d: un nng n mol 1 cht nguyn cht 0K --> T K, trong khong ny xy ra cc qu trnh bin i trng thi v iu kin P = const. Tnh S T?

21

Nhn xt: Gi tr S cht nguyn cht lun > 0, tr khi xt cho ion trong dung dch, c th c Sion < 0. 3.3 Bin thin entropy ca cc phn ng ha hc V S l hm trng thi v l i lng dung nn:

Nu iu kin chun (P = 1atm) v T=298K th:

V Skh >> Slng, Srn ==> c th cn c vo s mol kh 2 v ca phn ng nh gi ln cng nh l du ca S ca phn ng.

Hm th nhit ng. Tiu chun xt chiu ca qu trnh

H c lp: S 0 --> tiu chun t din bin v gii hn ca qu trnh. H khng c lp: gm h + Mi trng --> a v 1 h c lp mi bng cch gp h v mi trng thnh 1 h c lp. ==> tiu chun t din bin v gii hn ca h mi l: S + Smt 0.

22

Smt cha xc nh nhng c th a v cc thng s ca h bng cch tm 1 hm thay th cho c (S + Smt), hm thay th ny gi l hm th nhit ng. Thng gp h: ng nhit, ng p ==> c hm th ng nhit ng p. ng nhit, ng tch ==> c hm th ng nhit ng tch. 4.1 4.1.1 Hm th ng nhit ng p nh ngha Xt 1 h: T, P = const H thc hin mt bin i no .

==> tiu chun t din bin v gii hn ca qu trnh l:

4.1.2

ngha vt l ca G

23

 l phng trnh c bn ca nhit ng hc. Nu qu trnh l thun nghch --> cng l ln nht --> du =.

T v P = const => dT = 0 v dP = 0 c:

ngha ca G: G biu th cng hu ch ca qu trnh thun nghch ng nhit ng p. 4.2 4.2.1 Hm th ng nhit ng tch nh ngha Xt 1 h T, V = const, h thc hin 1 bin i no .

Tiu chun t din bin v gii hn ca qu trnh l:

4.2.2

ngha A 24

Nu qu trnh l thun nghch --> cng l ln nht --> du =.

T v V =const => dT = 0 v dV = 0 c:

ngha ca A: Bin thin th ng tch A biu th cng c ch ca qa trnh thun nghch ng nhit ng tch. Tm li tiu chun t din bin v gii hn ca qu trnh l:

Mi lin h gia G v A:

4.3

Bin thin th ng p

=> Qu trnh t din bin theo chiu lm gim G cho ti khi t gi tr Gmin: dG = 0; (G=0) d2G > 0 (G > 0) 4.3.1 Th ng p sinh chun ca 1 cht nhit T L s bin thin th ng p ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun v nhit T ca phn ng. 25

4.3.2

Tnh bin thin th ng p ca phn ng ha hc V G l hm trng thi v l i lng dung nn c:

Nu iu kin chun v 25C c:

G < 0: phn ng xy ra theo chiu thun G = 0: qu trnh cn bng G > 0: phn ng xy ra theo chiu nghch

5
5.1

Cc yu t nh hng n th ng p
nh hng ca nhit Xt h: Ch c bin i thun nghch, khng sinh cng c ch, c P = const.

26

Phng trnh Gibbs - Helmholtz cho php xc nh G theo T:

Thng xt iu kin chun (p = 1atm) v T = 298K:

5.2

nh hng ca p sut Xt h: Bin i thun nghch, khng sinh cng hu ch, T = const.

27

i vi cht rn v cht lng --> coi V = const khi P bin i (tr min P ln) nn:

i vi cht kh (coi l kh l tng) --> V =

nRT P

V d: Nn 0,5 mol kh l tng t P = 1 atm n P = 2 atm 25C. Hi qu trnh nn c t xy ra c khng?

5.3

nh hng ca thnh phn cc cht. Khi nim th ha

28

 ngha vt l ca i

Mt vi tnh cht ca th ho

29

=> th ho cng l tiu chun xt chiu v gii hn ca cc qu trnh (phn ng xy ra theo chiu gim th ho). 5.4 Mi quan h gia du G v ln H, S v T

V d

III H THNG CU HI N TP
Cu 1: Thit lp biu thc nh lng ca nguyn l th hai ca nhit ng lc hc. Cu 2: C phi mi qu trnh on nhit u l qu trnh ng entropi khng? Cu 3: Tnh cng, nhit v bin thin entropi trong qu trnh lm gin n ng p 820 lt kh N2 127C v 1 atm n th tch gp i. Xem N 2 l kh l tng v ly
C p , N 2 = 7cal .o 1.mol 1.

Cu 4: Tnh A, Q, U, H v S trong qu trnh nn thun nghch ng nhit 1 mol kh l tng 500C t 0,05 n 0,1 atm. Cu 5: Tnh S trong qu trnh un nng 2 mol NH3 t 100K n 1000K p = const.
4 1 Bit nhit dung ng p C p = 8,05 + 7.10 Tcal . .mol 1

Cu 6: Tnh S khi trn 2 mol N2 vi 1 mol H2 iu kin khng i. 30

Cu 7: Tnh S khi un 1 kg nc lng 0C n 200C. Ly nhit dung ca hi nc

C p = 0,469 cal / .gam

, nhit ha hi ca nc hh = 539 ,4cal / gam .

Cu 8: Tnh S khi chuyn 10 mol NH3 lng t -40C thnh NH3(k) 200C di p sut p = 1 atm, bit C p , NH
3

(l )

= 17 ,9cal / mol .K , C p , NH 3 ( r ) = 8,04 + 7.10 4 T + 5,1.10 5 T 2 ,

TNH 3 = 239 ,7 o K , hh = 5560 cal / mol .

Cu 9: Gii thch ti sao nhit c th t chuyn t vt nng sang vt lnh v nc t chy ra khi n tip xc vi vt c nhit cao hn 0C.

31

Chng 3 CN BNG HA HC
--- ---

I MC TIU
Cung cp cho sinh vin nhng kin thc c bn v cn bng ha hc, cc loi hng s cn bng ca mt phn ng ha hc cng nh mi quan h gia cc hng s ny. Cc yu t nh hng n bng s cn bng ca phn ng ha hc.

II NI DUNG CHI TIT

1
1.1

Phn ng thun nghch v phn ng 1 chiu

Phn ng thun nghch L phn ng xy ra theo hai chiu tri ngc nhau trong cng mt iu kin (c im ca phn ng thun nghch: khng tin hnh n cng m dn n cn bng).

Khi ly kh NO2 (hoc N2O4) nghin cu --> lun thu c ng thi c kh N2O4 hoc NO2) trong bnh ngay nhit thng do tn ti s chuyn ho gia hai kh trn --> gi phn ng trn l phn ng thun nghch. 1.2 Phn ng mt chiu L phn ng ch xy ra theo mt chiu xc nh. V d: Phn ng phn hu KClO3(xc tc MnO2): KClO3 --> KCl + 3/2O2 c im: Tin hnh ti cng. 1.3 Trng thi cn bng ha hc Mt phn ng khi t trng thi cn bng th: Xt v mt ng hc: vt = vn Xt v mt nhit ng: Gp = 0

32

Vy trng thi cn bng ho hc: L trng thi ca phn ng thun nghch khi tc phn ng thun bng tc phn ng nghch (hoc khi bin thin th ng p bng khng). c im ca trng thi cn bng ho hc L cn bng ng (phn ng vn xy ra theo 2 chiu ngc nhau nhng vt = vn). Ti trng thi cn bng thnh phn ca cc ch t khng thay i: cht tham gia phn ng mt i bao nhiu theo phn ng thun th li c sinh ra by nhiu theo phn ng nghch). Trng thi cn bng ch tn ti khi cc iu kin thc hin phn ng (C, t, p) khng i.

2
2.1

Phng trnh ng nhit Vant hoff. Hng s cn bng K

Thit lp phng trnh ng nhit Vant Hoff Xt phn ng: aA + bB <=> cC + dD T = const v A, B, C, D l cc kh l tng

Pi: p sut ring phn ca cc cht kh i = A, B, C, D

33

Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh ng nhit Vant Hoff 2.2 2.2.1 Phng trnh hng s cn bng K Hng s cn bng Kp

Pi: p sut cc kh trng thi CB. Kp khng c n v. Kp ch ph thuc vo bn cht phn ng v nhit . i vi 1 phn ng xc nh, T = const --> Kp = const --> gi l hng s cn bng ca phn ng. 2.2.2 Cc hng s cn bng khc

Ci: nng mol/lit cc cht trng thi cn bng. Kc ph thuc vo bn cht phn ng v nhit . i vi 1 phn ng xc nh --> Kc = f(T): Kc ch ph thuc vo nhit . 34

ni: s mol kh i trng thi cn bng. Kn ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng v tng s mol kh ca h khi cn bng.

KN ph thuc vo bn cht cc cht, T v P chung ca h khi cn bng. 2.2.3 Mi quan h gia cc hng s cn bng

35

36

2.3 2.3.1

Cc phng php xc nh hng s cn bng Xc nh theo thnh phn cc cht ti thi im cn bng V d: CaCO3(r) <=> CaO(r) + CO2(k)

2.3.2

Xc nh thng qua 1 s i lng nhit ng

V d: Tnh Kp ca phn ng sau 25C:

2.3.3

Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn V d 37

3
3.1

S chuyn dch cn bng. Nguyn l Le Chatielier

S chuyn dch cn bng Xt v mt nhit ng, khi phn ng t trng thi cn bng --> G = 0 -->
p
Kp =1 khi h ang trng thi cn bng nu ta thay i mt trong cc thng s trng

thi (P, T, C) ca h --> G 0 => cn bng b ph v, qu trnh s tin hnh theo chiu G < 0 t ti trng thi cn bng mi ng vi cc thng s mi (P, T, C). Xt v mt ng hc, khi phn ng t trng thi cn bng --> vt = vn => v = 0. Khi h t trng thi cn bng, ta thay i 1 trong cc thng s trng thi (P, C, T) => vt vn ==> qu trnh tin hnh theo chiu v > 0 t trng thi cn bng mi ng vi cc thng s mi. ==> gi l s chuyn dch cn bng. nh ngha: S chuyn dch cn bng l s chuyn t trng thi cn bng ny sang trng thi cn bng khc di nh hng ca cc tc ng bn ngoi (P, T, C) ln h. 3.2 nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant Hoff Xt phn ng: aA + bB <=> cC + dD P = const

38

 Khi nhit tng --> Kp tng --> cn bng chuyn dch theo chiu thun (chiu thu nhit). nhit). Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu nghch (chiu to

Khi nhit tng --> Kp gim --> cn bng chuyn dch theo chiu nghch (chiu thu nhit). Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu thun (chiu to nhit). Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi: Khi nhit tng th cn bng chuyn dch theo chiu lm gim nhit ca h l chiu thu nhit c HT > 0. Khi nhit gim th cn bng chuyn dch theo chiu lm tng nhit ca h l chiu to nhit c HT < 0. T phng trnh Vant Hoff suy ra:

39

3.3

nh hng ca p sut n s chuyn dch cn bng

V Kp khng ph thuc vo P --> thay i P th Kp = const nn: Nu n > 0: khi tng P --> KN gim ( gi Kp = const) => chuyn dch cn bng theo chiu nghch (lm gim s mol kh) v ngc li. Nu n < 0: khi tng P --> KN tng ( gi Kp = const) => chuyn dch cn bng theo chiu thun (lm gim s mol kh) v ngc li khi P gim --> KN gim --> cn bng dch chuyn theo chiu nghch (lm tng s mol kh). Nu n = 0 => P khng nh hng ti s chuyn dch cn bng. Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi: Nu P tng => cn bng chuyn dch theo chiu P gim (gim s mol kh < 0). Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh n > 0). 3.4 nh hng ca nng n

Nu tng CA, CB => cn bng chuyn dch theo chiu tng CC, CD ( gi = const) => cn bng chuyn dch theo chiu thun lm gim CA, CB.

KC

40

 Nu gim CA, CB => cn bng chuyn dch theo chiu gim CC, CD ( gi = const) => cn bng chuyn dch theo chiu nghch lm tng CA, CB.

KC

Nhn xt: Kt qu ca s chuyn dch cn bng l chng li thay i bn ngoi.

Nu tng Ci th cn bng chuyn dch theo chiu lm gim Ci v ngc li. 3.5 Nguyn l chuyn dch cn bng Le Chatielier Khi mt h ang trng thi cn bng, nu ta thay i 1 trong cc thng s trng thi ca h ( T, P hoc C) th cn bng s chuyn dch theo chiu chng li s thay i .

III H THNG CU HI N TP
Cu 1: Tnh hng s cn bng Kp ca phn ng: C(r) + O 2(k) CO2(k). Bit lc cn bng trong hn hp c 22,5% th tch kh CO2. Cu 2: Tnh cc hng s cn bng Kp, Kc, Kx ca h: 2HI H2 + I2. Bit rng lc ban u h gm 1 mol HI. phn ly ca n l = 0,2. Tnh thnh phn ca h lc cn bng. Cu 3: Chng minh hng s cn bng ca phn ng ch ph thuc vo trng thi u v trng thi cui ca phn ng, khng ph thuc vo din bin phn ng. Cu 4: Phn ng phn hy PCl5 250C v 1 atm c phn ly = 0,8. Nu a thm N2 vo h sao cho p sut khng i (1 atm) v p sut ring phn ca N 2 l 0,9 atm, ca cc cht trong phn ng bng 0,1 atm th phn ly thay i nh th no? Cu 5: Hng s cn bng ca phn ng: 2A(r) + B(h) C(h) + 2D(r), Kp = 2. Tnh khi lng cht D c to thnh nu pha hi trc phn ng gm 0,1 mol cht B v 0,08 mol cht C. p sut ca h lc cn bng l 1 atm. Phn t lng ca D l 75. Cu 6: Nu un 0,746 gam I2 v 0,0162 gam H2 n 603K trong bn kn c th tch l 1 lt. Khi t n cn bng s to thnh 0,721 gam HI. Nu thm vo hn hp u 0,1 gam I2 v 0,005 gam H2 s thu c bao nhiu gam HI?

41

Chng 4 CN BNG PHA

------

I MC TIU
Sinh vin nm c mt s khi nim c bn v cn bng pha. Gip sinh vin nm c cc quy tc c bn trong cn bng pha c bit l cn

bng pha trong h 1 cu t.

II NI DUNG CHI TIT

1 Mt s khi nim
1.1 Pha Pha () l phn ng th ca h c thnh phn, tnh cht l hc, tnh cht ho hc ging nhau mi im ca phn ng th v c b mt phn chia vi cc phn khc ca h. Pha ch gm 1 cht gi l pha nguyn cht (pha n) cn pha gm 2 cht tr ln --> gi l pha phc tp. H gm 1 pha --> h ng th. H 2 pha -> h d th. V d: H gm H2O + H2O lng + H2O hi => gm 3 pha: rn, lng, hi. H gm CaCO3(r), CaO(r),CO2(k) --> 3 pha: 2 pha rn + 1 pha kh 1.2 Cu t Cu t l phn hp thnh ca h c th c tch ra khi h v tn ti c bn ngoi h. S cu t trong h k hiu l R V d: dung dch NaCl gm 2 cu t l NaCl v H2O --> R = 2 1.3 S cu t c lp K S cu t c lp (K) l s ti thiu cc cu t xc nh thnh phn ca tt c cc pha trong h. 42

Nu cc cu t khng phn ng vi nhau v nu pha c thnh phn khc nhau th K = R (trong h khng c phng trnh lin h nng cc cu t) V d: dung dch NaCl => R=K=2. Nu cc cu t tng tc vi nhau v nm cn bngvi nhau --> chng khng cn c lp vi nhau na --> K = R-q q: s h thc lin h gia cc nng (q c th l phng trnh hng s cn bng, iu kin u v nng ca cc cu t). V d: H gm 3 cu t HCl, Cl2, H2 u l cc cht kh c tng tc, nm cn bng vi nhau: 2HCl(k) <=> H2(k) + Cl2(k).

=> bit c nng ca 2 cu t s bit c nng ca cu t cn li. Vy h c: R = 3, q = 1, ==> K = R-q = 2 Nu gi thit ban u h ch c HCl (hoc cho t l mol H2:Cl2 ban u) => q = 2 => K=1. 1.4 Bc t do ca h C Bc t do ca h (C) l s ti thiu cc thng s trng thi cng (P, T, C) xc nh trng thi cn bng ca 1 h (l s thng s trng thi cng c th thay i 1cch c lp m khng lm bin aei s pha ca h). V d: H2O(l) <=> H2O(k) ==> cn bng c 2 pha ==> C = 1 v: + C th thay i 1 trong 2 thng s P hoc T m khng lm thay i s pha ca h. + Hoc: mt nhit xc nh th P hi H2O nm cn bng vi H2O lng l xc nh, tc l ch cn bit 1 trong 2 thng s T hoc P th xc nh c trng thi cn bng ca h. 1.5 Cn bng pha Cn bng trong cc h d th, cc cu t khng phn ng ho hc vi nhau nhng xy ra cc qu trnh bin aei pha ca cc cu t => cn bng pha.

43

2 Quy tc pha Gibbs

Xt h gm R cu t 1,2, ... R c phn b trong pha (, , , ..., pha). 2.1 iu kin cc pha nm cn bng vi nhau m bo cc cn bng sau: - Cn bng nhit: nhit cc pha bng nhau:

- Cn bng c: p sut cc pha bng nhau:

- Cn bng ho: th ho ca mi cu t trong cc pha bng nhau:

2.2

Quy tc pha Gibbs - Cc thng s trng thi cng xc nh trng thi ca h l T, P, C. Gi Ni l nng mol phn ca cu t i trong 1 pha th N1 + N2 + N3 + ... + Ni = 1 => Vy xc nh nng ca R cu t trong 1 pha cn bit nng ca (R-1) cu t. V c pha => xc nh nng ca R cu t trong pha th s nng cn bit l (R-1). T s thng s trng thi cng xc nh trng thi ca h l (R-1) + 2. trong s 2: biu th 2 thng s bn ngoi l T v P xc nh trng thi ca h. V cc pha nm cn bng vi nhau => cc thng s khng c lp vi nhau na: c lin h vi nng m khi cn bng th ca mi cu t trong cc pha phi bng nhau (iu kin cn bng ho).

44

=> Mi cu t c ( -1) phng trnh lin h ==> R cu t c c R( -1) phng trnh lin h gia cc thng s. Nu c thm q phng trnh lin h nng cc cu t, v d: khi c phn ng ho hc gia cc cu t th s phng trnh lin h cc thng s trng thi cng ca h l: R( -1) + q Bc t do ca h = Cc thng s trng thi s phng trnh lin h gia cc thng s.

Nhn xt + Khi K tng => C tng, tng v C gim. + Bc t do C 0 => K + 2 + Nu trong iu kin ng nhit hoc ng p th: C =K - + 1 (Nu phng trnh c n = 0 => P khng nh hng ti phn ng --> dng phng trnh ny). + Nu h va ng nhit va ng p th C = K- V d 1: Xt h 1 cu t (R = K = 1), v d nc nguyn cht. - Nu trng thi hi => = 1 => C = K- +2 = 1-1+2 = 2 => trng thi ca hi nc c xc nh bi 2 thng s trng thi cng l T v P. - Nu hi nc nm cn bng vi nc lng th = 2 => C = 1-2+2 = 1 => trng thi ca h gm H2O lng v hi c xc nh bi 1 trong 2 thng s l T hoc P (v 1 nhit xc nh th P ca hi nc l xc nh) V d 2: Xt h gm: Mg(OH)2(r) <=> MgO(r) + H2O(k) =2 pha rn + 1 pha kh = 3 pha C = R-q+2 = 3-1-3+2 = 1 => c php thay i 1 trong 2 thng s l T hoc P m khng lm thay i s pha ca h hoc trng thi cn bng c xc nh bng 1 trong 2 thng s T hoc
PH 2O ( h ) .

3 Cn bng pha trong h 1 cu t

3.1 Cn bng pha trong h 1 cu t Xt h gm 1 cht nguyn cht, khi trong h c 2 pha nm cn bng nhau: 45

=> C= K- +2 =1-2+2 =1 (R = K-1) trng thi cn bng gia hai pha c c trng bi hoc T hoc P, tc l nu 1 trong 2 thng s trng thi l P hoc T bin i th thng s kia phi bin i theo: p = f(T) hoc T = f(P). C th l: - P = const => cht nguyn cht nng chy, si hoc chuyn trng thi tinh th 1 nhit nht nh, c gi l nhit chuyn pha Tcf, nhit ny khng b bin i trong sut qu trnh chuyn pha. Khi p sut thay i => Tcf thay i theo. V d: P = 1atm, nc nguyn cht ng c 0C v si 100C P = 2atm, nc nguyn cht ng c 0,0076C v si 120C - T = const, hi nm cn bng vi lng v rn c P nht nh gi l P hi bo ho (hi c goi l hi bo ho). Cc ng cong biu th s ph thuc ca Phi bo ho ca pha rn vo nhit , ca pha lng vo nhit v nhit nng chy vo P ct nhau ti 1 im gi l im ba, im ba ny ba pha rn lng hi (R, L, H) nm cn bng vi nhau:

Khi C=1-3+2 =0 => v tr im ba khng ph thuc vo T v P m ch ph thuc vo bn cht cht nghin cu. 3.2 nh hng ca p sut n nhit nng chy, si v chuyn dng tinh th ca cht nguyn cht V h 1 cu t nn th ha ng nht vi th ng p mol (Gi = i ). Khi T, P khng i iu kin cn bng gia hai pha v l:

V h c C = 1 nn nu mt thng s bin i, v d p sut bin i mt lng dP th mun hai pha tn ti cn bng, nhit cng phi bin i mt lng dT. Khi th ng p mol phi bin i: 46

3.3

nh hng ca nhit n p sut hi bo ha ca cht nguyn cht

47

III H THNG CU HI N TP
Cu 1: Thit lp phng trnh Claypeyron Clausius. Cu 2: Nhit nng chy ca naphtalen 81,1C l Hnc = 35,5 cal/g. Tnh bin thin ca nhit nng chy khi lm thay i p sut 1 atm, nu bin thin th tch ring ca naphtalen khi chuyn t trng thi rn sang trng thi lng l 0,15 ml/g. Cu 3: Khi lng ring ca thic rn v lng nhit nng chy 231,9C tng ng bng 7,184 v 6,998 g/cm3. Nhit nng chy ca thic bng 1690 cal/mol. Xc nh nhit nng chy di p sut 100 atm. Cu 4: Tnh p sut ca qu trnh chuyn than ch thnh kim cng 25C nu bit G v V ca qu trnh l 685 cal/mol; -1,19 cm3/mol p = 1 atm. Cu 5: p sut hi bo ha ca cht A 550C l 0,6 mmHg. Tnh p sut hi bo ha ca n 750C. Ly nhit ha hi Hhh = 38,518 cal/mol.

48

Chng 5 DUNG DCH

--- ---

I MC TIU
Sinh vin nm c mt s khi nim c bn v dung dch, ng lng v cch tnh ng lng. Xc nh c ha tan ca 1 cht v cc yu t nh hng n ha tan. Sinh vin cng nm c cc tnh cht c trng ca dung dch.

II NI DUNG CHI TIT

1 H phn tn
1.1 nh ngha L h gm 2 hay nhiu cht trong cht ny c phn b trong cht kia di dng nhng ht rt nh. - Cht phn b c gi l cht phn tn, cht kia l mi trng phn tn. Cht phn tn v mi trng phn tn c th 1 trong 3 trng thi: rn, lng hay hi. V d: ng tan trong nc => ng l cht phn tn, H2O l mi trng phn tn - Da vo kch thc ca ht phn tn, chia lm 3 h phn tn: 1.1.1 H phn tn th Kch thc ht t 10-7-10-4 m - c im: Khng bn,cht phn tn d tch ra khi mi trng phn tn. - C 2 dng: + Huyn ph: cht phn tn l rn, pha phn tn l lng. V d: nc ph sa. + Nh tng: cht phn tn l lng, mi trng phn tn cng l lng. V d: sa c ln nhng ht m l lng. 1.1.2 Dung dch keo
Kch thc ht t 10-7 10-9 m

49

c im: tng i bn. 1.1.3

Dung dch thc (dung dch) Kch thc ht 10-10 m (bng kch thc phn t hoc ion), trong cht phn tn v mi trng phn tn c phn b vo nhau di dng phn t hoc ion, gia chng khng cn b mt phn chia, to thnh 1 khi ng th gi l dung dch thc. Cht phn tn c gi l cht tan, mi trng phn tn c gi l dung mi. c im: H ny rt bn.

1.2

Cc loi nng

2 ng lng
Trong cc phn ng ho hc, cc cht tc dng va vi nhau theo nhng s phn khi lng tng ng gi l ng lng. Chn ng lng ca H lm n v H=1 2.1 nh ngha ng lng - ng lng ca mt cht hoc ca 1 nguyn t l phn khi lng ca cht hoc nguyn t tc dng va vi 1 ng lng ca H. V khng phi mi cht u phn ng vi H => nh ngha c m rng nh sau: ng lng ca 1 nguyn t hay 1 hp cht l s phn khi lng ca n tc dng va vi 1 ng lng ca 1 cht bt k.

50

2.2 2.2.1

Cch tnh ng lng ng lng ca nguyn t

Vi nguyn t c nhiu ho tr khc nhau s c nhiu ng lng v ng lng ca chng gn vi 1 phn ng c th m chng tham gia. 2.2.2 ng lng ca hp cht

2.3

nh lut ng lng

51

3 ha tan
3.1 Qu trnh ha tan. Nhit ha tan ca mt cht Qu trnh ho tan (khng phi l qu trnh trn ln) gm qu trnh: + Qu trnh phn tn cht tan (di dng nguyn t, phn t, ion) vo trong khp th tch dung mi. +Qu trnh tng tc gia cc phn t ca dung mi vi cc phn t ca cht tan => to thnh dung dch (hp cht ho hc) Hp cht ho hc to thnh gi l hp cht sonvat, nu dung mi l nc th gi l hp cht hydrat. => Qu trnh ho tan c s ph v lin kt cng loi to lin kt khc loi v c th biu din bng s :

52

3.2

nh hng ca bn cht cht tan v dung mi n S

3.3

nh hng ca nhit n tan

53

3.4

nh hng ca P (i vi cht kh). nh lut Henry

4 Tnh cht ca dung dch

54

4.1

p sut hi bo ha ca dung dch. nh lut Rault I

4.1.1

p sut hi bo ha ca dung mi nguyn cht ( P o ) 1

4.1.2

p sut hi bo ha ca dung dch P1

55

4.1.3

nh lut Rault I

4.2 4.2.1

Nhit si v nhit ng c ca dung dch. inh lut Rault II Nhit si ca dung dch

56

4.2.2

Nhit ng c ca dung dch cha cht tan khng bay hi

4.3 4.3.1

S thm thu v p sut thm thu S thm thu

4.3.2

p sut thm thu

57

III H THNG CU HI N TP
Cu 1: i lng mol ring phn l g? Cu 2: i lng mol ring phn biu kin l g? Cu 3: Khi lng ring ca dung dch 25% NaBr trong nc bng 1,223 g/cm3. Hy biu th thnh phn dung dch ny qua phn mol, molan v mol/lit dung dch. Cu 4: Trong 1 lt dung dch cha 5,65 mol NaCl v 0,65 mol Na2SO4. Hy tnh nng molan ca mui, bit khi lng ring l = 1,25 g/cm3. Cu 5: Xc nh khi lng ring ca dung dch v nng % (khi lng) khi ha tan 25 gam CuSO4.5H2O v 175 gam H2O. Cu 6:Hy xc nh khi lng ring ca dung dch 40% CH3OH trong nc. Bit th tch mol ring phn ca H2O v CH3OH tng ng bng 17,5 v 39 cm3. Cu 7: Vit phng trnh biu din s ph thuc ca th tch mol ring phn ca dung mi qua khi lng ring ca dung dch.

58

Chng 6 DUNG DCH CHT IN LY

------

I MC TIU
Sinh vin nm c nhng c trng c bn ca dung dch in ly v in ly. Sinh vin bit c mi quan h gia in ly v hng s in ly trong dung

dch cht in ly. Sinh vin nm c thuyt axit-baz ca Bronsted v cc phng php xc nh

pH ca cc dung dch axit-baz-mui.

II NI DUNG CHI TIT

1 Tnh cht ca dung dch in ly
1.1 Cht in ly

1.2

Cht in ly mnh

59

1.3

Cht in ly yu

1.4

Tnh cht bt thng ca dung dch cht in ly so vi dung dch cht khng in ly

2 in ly

2.1

nh ngha

60

2.2

Cch xc inh

61

3 Cn bng trong dung dch cht in ly yu

3.1 Hng s in ly

3.2

Mi lin h gia K v . nh lut pha long Ostwald

62

3.3

Dch chuyn cn bng trong dung dch cht in ly yu

4 Thuyt axit-baz ca Bronsted

4.1 nh ngha axit-baz

63

4.2

Tch s ion ca nc ch s hydro (pH)

4.3
4.3.1

Hng s in ly axit-baz

Hng s in ly ca axit Ka

4.3.2

Hng s in ly ca baz Kb

64

4.4

Mi lin h gia Ka, Kb ca mt cp axit-baz

4.5

Ch s hydro pH

65

5 Tnh pH ca cc dung dch axit-baz-mui

5.1 Tnh pH ca dung dch axit mnh 1 bc

5.2

Tnh pH ca dung dch baz mnh 1 bc

66

5.3

Tnh pH ca axit yu 1 bc

67

5.4

Tnh pH ca baz yu 1 bc

5.5

Tnh pH ca dung dch mui

68

69

5.6

Tnh pH ca dung dch axit nhiu bc

70

6 Cn bng trong dung dch cht in ly t tan

6.1 Tch s ha tan ca cht in ly t tan

6.2

Mi quan h gia tch s tan Ks v ha tan S

71

6.3

iu kin to thnh kt ta v ha tan kt ta

III H THNG CU HI N TP
Cu 1: Cho tch s tan ca PbF2 l 4.10-9. Tnh ha tan ca PbF2 trong:
a. H2O

b. Dung dch NaF 0,1M.

c. Dung dch HCl 0,1M (khng k nhng xem HF phn ly 1% trong dung dch c

pH = 1). 72

Cu 2: Mt dung dch axit yu HA 0,01M c K a =1,47 .10 3 . Trong H2O phn ly theo phng trnh: HA + H 2O H 3O + + A Tnh h s phn ly trong 2 trng hp sau: a. Khng n h s hot . b. n h s hot . Cu 3: Dung dch cha 8 g NaOH trong 1000g nc ng c -0,677C. Hng s nghim lnh ca nc l 1,86. Hy nh in ly . Cu 4: Xc nh p sut thm thu ca 1 lt dung dch cha 50 g ng saccaro 0C. Cu 5: Hy xc nh nhit ng c ca dung dch cha 40% ru C2H5OH trong nc, bit khi lng ring ca dung dch bng 0,935g/cm3. Hng s nghim lnh ca nc l 1,86. Cu 6: Xc nh p sut thm thu ca dung dch anilin trong ete etylic 10C, nu p sut hi ca dung dch bng 279,5 v ca ete nguyn cht l 291,7 mmHg. T khi ca dung dch l 0,737 g/cm3.

73

Chng 7 NG HA HC
--- ---

I MC TIU
gin. Sinh vin nm c cc quy lut ng hc v s nh hng ca nhit , p sut, Sinh vin nm c nhng khi nim c bn v tc phn ng, hng s tc phn ng, phng trnh tc , bc phn ng, cc quy lut ng hc ca phn ng n

dung mi, cht xc tc ln tc phn ng.

II NI DUNG CHI TIT

1 Khi nim v vn tc phn ng
nh ngha vn tc phn ng

74

Cc yu t nh hng ln vn tc

Thuyt va chm hot ng

2.1

Ni dng

2.2

Phn b Boltzman

3 nh hng ca nng cc cht tham gia phn ng n vn tc v nh lut tc dng khi lng
nh lut tc dng khi lng

75

Bc phn ng

76

nh hng ca nhit ln vn tc phn ng

Quy tc Vant Hoff

Phng trnh Arrhenius

77

nh hng ca xc tc ln vn tc phn ng
nh ngha

78

c im xc tc

Gii thch c ch ca xc tc i vi xc tc ng th

79

i vi xc tc d th

6 Cc phng trnh ng hc ca phn ng ha hc

Phn ng bc mt

80

Cc phn ng bc hai

81

III H THNG CU HI N TP
Cu 1: Phn ng din ra nh sau: A + 2B 3C. Biu din phng trnh tc ca phn ng ln lt theo k, A, B, C, nu phn ng l phn ng n gin. Cu 2: Trn cht A vo cht B v C theo lng bng nhau v bng 1 mol/l. Sau 1000 giy mt na cht A phn ng. Hi sau 2000 giy cht A phn ng bao nhiu? Nu phn ng l: a. Bc nht. b. Bc hai. Cu 3: Trong phn ng CH3COCH3 C2H4 + CO + H2. p sut chung bin i theo thi gian nh sau: t(s) P(mmHg) 0 312 390 408 777 488 1195 562
k

Chng minh phn ng l bc nht v tnh hng s tc phn ng nhit th nghim (V = const). Cu 4: H s nhit ca phn ng bng 3,5. 15C hng s tc ca phn ng ny bng 0,2 giy-1. Tm hng s tc 40C. Cu 5: Hng s tc phn ng x phng ha este bng kim 282,8K l 2,37 cn 286,6K l 3,204 (mol-1l.ph-1). nhit no th hng s tc phn ng bng 4. Cu 6: Tnh hng s tc dime ha etylen 2C2 H 4 C4 H 8 673K. Bit H* = 32730 cal/mol, S* = 33 cal/mol . Cu 7: Tnh hng s tc phn ng C5 H 5 N + CH 3 I C5 H 5 CH 3 + I p sut 1000 atm, 50C, nu
k p = atm =1 , V * = 38 ml / mol . 1
+

Cu 8: C ch v ng ha hc ca phn ng xc tc ng th trong dung dch. Th no l cht trung gian Arrhenius v cht trung gian Van't Hoff, chng khc nhau nh th no?

82

Chng 8 CC QU TRNH IN HA
--- ---

I MC TIU
Sinh vin nm vng l thuyt c bn nht v mt s bi tp vn dng vn dng trong cc hc phn ha hc khc. Nm c mt s thuc tnh ca dung dch in ly. Bit v hiu c quy lut nhit ng lc hc ca cc qu trnh in ha trn

ranh gii pha in cc dung dch.

II NI DUNG CHI TIT

1 Nguyn tc bin ha nng thnh in nng
Phn ng oxy ha kh

83

Nguyn tc bin ha nng thnh in nng

Cu to hot ng ca pin Cu-Zn Cu to

Hot ng

2 Cc loi in cc
in cc kim loi

84

in cc tr nhng trong dung dch cha cp oxy ha kh

in cc kh

85

3 Sut in ng ca pin
nh ngha

Cc yu t nh hng n E cng thc Nernst

86

4 Th in cc (th kh)
Cp oxy ha kh

Th kh

87

88

Cc yu t nh hng n th in cc

89

5 Chiu v trng thi cn bng ca phn ng oxy ha kh xy ra trong dung dch nc

Chiu ca phn ng oxy ha kh

90

Trng thi cn bng ca phn ng oxy ha kh

91

6 Qu trnh in phn
nh ngha

S phn cc

92

S phn cc v nng

S phn cc ha hc

S phn cc in ha

Th phn hy

S in phn cht in ly nng chy

93

in phn dung dch cc cht in ly

Qu trnh catod

Qu trnh anod

94

III H THNG CU HI N TP
Cu 1: Ghp in cc in th in cc
+

Ag + / Ag

vi in cc calomel 1N 25C th sc in ng pin o

c l 0,236 V, vi in cc calomel l cc m. Vit phn ng xy ra trong pin v tnh

Ag / Ag

. Bit Calomel = 0,28V .

Cu 2: Tnh hng s cn bng ca phn ng sau y 25C.

ZnSO 4 + Cd CdSO 4 + Zn
o Bit Zn
2+

/ Zn

o = 0,763 V ; Cd 2+ / Cd = 0,403V

Cu 3: Cho pin Ag / Ag + ( a = 0,01) // Zn 2 + ( a = 0,1) / Zn a. Vit phn ng ha hc ca pin. b. Tnh sc in ng ca pin 25C v cho nhn xt.
o Bit Ag
+

/ Ag

= 0,799 V

Cu 4: Cho pin Ag / Ag 2 SO4 ( r ) / H 2 SO4 ( m ) / H 2 (1atm ) / Pt a. Vit phn ng cc in cc v phn ng ca pin.

b. Tnh Epin 25C nu m = 0,1.
E pin = 0,62 V

(khng k h s hot ).

Cu 5: Xc nh hiu sut dng in nu khi cho 25 ampe gi i qua dung dch ZnSO 4 th thu c 22,5 g Zn trn catod. Cu 6: Tnh lng Cu c gii phng trn catod nu cho mt dng in cng 1,5A i qua dung dch CuSO4 trong 12 pht. Cu 7: Cn phi in phn trong bao lu mt dung dch NiSO4 vi cng dng l 2A thu c hon ton Ni trn catod bit rng hiu sut dng bng 90%, th tch dung dch NiSO4 l 0,5 lt v nng dung dch l 0,1 N.

95